Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



United States Patent DETERGENT SULPHONIC ACID AND SUL-- PHATE SALTS OFCERTAIN AMPHOTERIC DETERGENTS Hans S. Mannheimer, New York, N. Y.

N0 Drawing. Application January 5, 1956, Serial No. 557,458

8 Claims. (Cl. 260-401) This invention relates to novel compositions andto methods for producing them. In one of its more specific aspects, theinvention is directed to the method of making and to novel derivates ofmetal salts of substituted amido, amino acids, to which I shallhereinafter refer to as amino acid metal salts.

Said amino acid metal salts have been found useful as detergent,foaming, wetting, emulgating, emulsifying and dispersing agents. Theyare surface active agents, and serve as excellent synthetic detergents,dye assistants and softeners in the textile and related fields.

Said amino acid metal salts, employed as starting materials in thepractice of this invention, have the following general Formula I:

in which R is an organic radical, which, if connected to a carboxylgroup, provides a monocarboxylic acid, and said radical contains atleast 4 carbon atoms and for most purposes is a hydrocarbon radical of4-l8 carbon atoms; R1 is hydrogen or an aliphatic hydrocarbon radicalhaving 1-4 carbon atoms, such as CI-I3, --C2H5, C3H7, and -C4H9 or anyone of said radicals having one or more of the hydrogens thereof whichhas been hydroxy substituted, illustrative examples of which are or anyone of said radicals, but of 24 carbon atoms and whose hydrogens havebeen either unsubstituted or hydroxy substituted and having a singleether (--O) or keto (-CO) linkage therein, illustrative examples ofwhich are -C2H4-OCH3, C2H4OC2H4OH,

R2 is a hydrocarbon group having 14 carbon atoms, such as --CH2, C2H4,C3He and -C4Hs-, or any one of the aforesaid groups, any one or more ofwhose hydrogens has been hydroxy substituted, illustrative examples ofwhich are and preferably such hydrocarbon groups of 3 and 4 carbonatoms, wherein one or more of the hydrogen atoms thereof not attacheddirectly to the terminal carbon atoms of said groups have been hydroxysubstituted, or any one of said groups, but of 2-4 carbon atoms andwhose hydrogens have been either unsubstituted or hydroxy substitutedand having a single ether (0) or keto (-CO-) linkage therein; M is ametal and preferably an alkali metal and, for most purposes, is sodiumor potassium.

Said amino acid metal salts may be produced in a number of differentways:

One of the methods which may be employed is to first react an hydroxydiamine with an organic acid in the H 2,781,382 Pe.tented Feb. 12, 1957molecular proportion of 1 to 1. When approximately 1 mole proportion ofwater of reaction has been formed and the acid number of the mass iszero, the reaction is terminated, and the resulting reaction mass underspecific and controlled conditions is reacted with a metal salt of amonohalomonocarboxylic acid to provide an amino acid metal salt definedin Formula I.

The organic acid reacted with said diamine is one containing a singleCOOH group or any of the available anhydrides of said acids and by theterm monocarboxylic organic acid as used herein, I mean to include boththe acid and the anhydride thereof which I regard as the equivalent ofthe acid. These acids may be: the aliphatic open chain saturated orunsaturated fatty acids as well as said fatty acids containing hydroxyor keto groups and/or other substituents, such as aryl radicals, as forexample, acids of the type of Twitchell fatty acids; cycloaliphaticcarboxylic acids preferably containing no more than 4 condensed nucleiand examples of which are hexahydrobenzoic, resinic, and naphthenicacids; heterocyclic aliphatic carboxylic acids, such as the variouspyridine carboxylic acids.

While carboxylic acids having any number of carbon atoms may beemployed, I prefer to employ those having at least 5 carbon atoms andpreferably 5-l9 carbon atoms in straight chain relationship. The acidswhich I employ may be derived from a number of different sources. Amongsome of them are the acid components chosen from oil or fats of animal,marine-or vegetable origin and these include; the acids of cocoanut,palm kernel and palm oil, also from soy bean, linseed, olive, rapeseed,cottonseed, peanut and castor oil which contain large proportions ofunsaturated hydroxy fatty acids and also the acids derived from tallow,fish and seal oils, Whale or shark oils and the hydrogenated acids fromthese sources. Moreover, the synthetic high molecular weight fattyacids, obtained by the oxidation of paraffin wax and similar highmolecular weight hydrocarbons by means of gaseous oxidizing agents maybe employed. In addition the acid may be one of the resinic acids, suchas abietic acid, or the naphthenic acids and long chain fatty acidshaving an aromatic hydrocarbon radical connected directly with thealiphatic chain (Twitchell fatty acids) as are obtainable from oleic,ricinoleic, linoleic and similar unsaturated fatty acids. Instead ofemploying mixture of acids from oil, fats and resins, single acids maybe used, for example, caproic, myristic, heptylic, caprylic, undecylic,lauric, palmitic, stearic, behenic, arachic, cerotic, oleic, erucic,linoleic, linolenic, r-icinoleic and hydroxystearic acids.

Of the aforesaid diamines I prefer to employ aminoethylethanolaminehereinafter referred to as reactant A. Because it is commerciallyavailable in large quantities, its use provides for efficient productionof some of the starting materials.

Examples of some of the other diamines which may be employed in theproduction of starting materials are methyl amino isopropyl isopropanolamine (CHaNHCsHsNHCsI-IsOH) amino isobutyl isobutanol amine(NHaCrHsNI-ICrHaOH), amino hydroxypropyl propane diol amine,

(NH2C3H5OHNHCsH4(OH )2) propyl amino ethoxy ethyl ethoxy ethanol amine(C3H'INHC2H4OC2H4NHC2H4OC2H4OH) butyl amino hydroxy propyl acetol amine,

(C4H9NHC3H5OHNHCH2COCH2OH) ethyl amino propanone ethanol amine(C2H5NHCH2COCH2NHC2H4OH) respectively, hereinafter referred to asreactants B, C, D, E, F and G.

The reactants AG respectively may be produced by employing a number ofdifferent classical methods well known to the art. One method consistsessentially in reacting ammonia with a compound which is the dichlorideof the R2 group between the two nitrogens and has formula Cl-R2-Cl, andsubsequently treating the diamine produced with caustic soda to removeHCl which is attached. Then the resultant diamine is reacted with acompound of the formula ClRzOH, and if R1 is other than hydrogen,another reactant R1Cl is used. Again, the hydrochloride is removed. Inthis manner, the various diamines employed in the production of mystarting materials may be produced and are of the following formula:

in which R1 and R2 have heretofore been defined.

One of the well-known commercial methods employed in the production ofsaid diamines whose general formula is above set forth is predicatedupon the reaction of epoxy compounds, such as, ethylene oxide, propyleneoxide, etc., with ammonia to form theintermediate diamine which issubsequently reacted with additional epoxy compound in the presence ofwater.

Among some of the salts of the halo acids which may be employed are thesodium and potassium salts of monochloracetic acid, monochlorproprionicacid, monochlorlactic acid, monochlorhydroxyacetic acid obtainable fromdi-chloracetic acid, monochloracetoacetic acid, monochlorethoxyaceticacid, etc.

One of the general types of method which may be employed for theproduction of some of these starting materials consists in firstreacting one mol of a monocarboxylic acid having at least 4 carbon atomsin its radical connected to its COOH group with one mol of one of saiddiamines, examples of which are reactant-s A-F, until only approximately1 mol of water has been removed. In carrying out this reaction themixture is first heated to about 110-180 C. in vacuum of 90-130 mm. ofmercury pressure until one mol of water of reaction has been producedand removed. (All of the terms mm. and mm. pressure as used in thisentire description are intended to mean mm. of mercury pressure.) Thereaction mass is then allowed to cool to room temperature and is then atelevated temperatures reacted with a monohalocarboxylic acid in thepresence of 2 mols of caustic soda in aqueous solution. in one of itspreferred forms one mol of said reaction mass is added to an aqueoussolution containing one mol of the monohalocarboxylic and 2 mols ofcaustic soda, which solution prior to the addition has been prepared andmaintained at a temperature no greater than C. The mix is heated to atemperature of 95 C. until the pH has been reduced from about 13 to8-8.5 and there is no further change in pH upon continued heating atsaid temperature.

Another method which may be employed for producing starting materials ofFormula I in the practice of this invention is as follows:

The reaction mass of the monocarboxylic acid and the diamine, an exampleof which is product X, is heated to 90100 C. and there is graduallyadded thereto an equi-molecular proportion of monohalomonocarboxylicacid, such as monochloracetic acid, whereupon exothermic reaction occursand the temperature rises from 90-100 C. to about ISO-160 C. Theresultant is allowed to cool to 100 C. and is then dissolved in water.To this solution is added an aqueous solution containing 2 mols ofcaustic soda for each mol of monochloracetic acid previously used. Thismass is stirred for about there are added 80.5 parts of chlorhydrin.

4 15 minutes at a temperature of about 60 C. The resultant product is areaction product as defined in Formula I.

Still another method which may be employed for the production of theintermediate, known herein as product X, is to react an acid chloride,having the general formula RCOC1, R being heretofore defined, with thediamine in the presence of water and caustic soda.

The following are illustrative examples given merely for the purposes ofspecifically illustrating how some of the starting materials employed inthe practice of the present invention may be produced, all parts beinggiven by weight unless otherwise specified:

EXAMPLE A 200 parts of lauric acid and 104 parts of reactant A areplaced in a reacting vessel and are heated sufficiently to melt thelauric acid whereupon an agitator located therein is started and mixesand maintains these components in mixed condition. While beingconstantly agitated the mix is heated under vacuum of about 110 mm.pressure for about 3 hours While gradually raising the temperature to170 C. During this period 18 parts of water have been formed anddistilled off, leaving behind a reaction mass, having an acid number ofapproximately zero. Then this reaction mass, herein known as product X,is allowed to cool to room temperature .and the entire mass is added toa previously prepared solution produced by adding 96 parts ofmonochloracetic acid and parts of caustic soda to 300 parts of water.This solution was prepared and maintained at a temperature below 20 C.before the addition of said reaction mass. This mixture is heated to C.and maintained at this temperature for 2 hours. During this period thepH of the mix is reduced from approximately 13 to 8-8.5. At the end ofthis period the pH of this mass is no longer subject to change bycontinued heating at said temperature and a sample of the resultingproduct is water soluble to a sparkling clear solution. At the end ofthis period the mass consists chiefly of a water solution of one of mystarting materials, hereinafter known as product A and having thefollowing formula:

To the aqueous mass produced under the method of Example A andcontaining 389 parts of my product A, whose formula is defined therein,there is added an aqueous solution consisting of 40 parts of causticsoda dissolved in 40 parts of water. Then to said mixture This mixturewhich at this stage is at room temperature is heated over a period of 1hour to 95 C. The mass is subsequently maintained at this temperature of95 C. until thereis no change in pH, this taking approximately 2 to 3hours. The reaction mass consists essentially of an aqueous solution ofanother one of my starting. materials, hereinafter known as product B,and having the formula which is the same as that of Example A, exceptthat C2H4OC2H4OH is substituted for C2H4OH.

EXAMPLE C 172 parts of capric acid and 104 parts of reactant A areheated and reacted under the same condition as given in Example A, and240 parts of the reaction mass produced thereby are introduced into asolution of parts of monoehlorpropionic acid and 80 parts of causticsoda in 300 parts of water prepared and maintained below 20 C. Theresulting mixture is then heated under the same conditions as outlinedin: Example A until the resulting product forms sparkling clear aqueous,solutions and is no longer subject to pH change in continued heating.At-the end of this period the massconsists chiefly of an aqueoussolution of one of my starting materials, hereinafter known as productC, and having the formula the same as that of Example A, except thatC9H19 is substituted for C11H23 therein, and C2H4 for the CH2.

EXAMPLE D 282 parts linseed fatty acid and 104 parts reactant A aretreated in the same manner as described in Example A. The entirereaction mass is then processed with an aqueous solution of 96 partsmonochloroacetic acid and 80 parts of caustic soda previously made andmaintained below 20 C. and subsequently processed in the manner ofExample A to produce starting material, hereinafter known as product D,and having the same formula as that of Example A except that C1'TH31 issubstituted for C11H2a therein.

EXAMPLEE 116 parts of caproic acid and 104 parts of reactant A arecondensed in the manner as described in the previous examples and theresulting reaction mass is subsequently processed in the same manner asthat set forth 1n the processing of that of Example A.

The reaction product has the same formula as that of Example A, exceptthat C5H11 is substituted for C11H23 therein, and is hereinafter knownas product E.

EXAMPLE F 284 parts of stearic acid and 104 parts of reactant A areheated in the like manner as described in previous examples, and theresulting reaction mass is then introduced into an aqueous solution of110 parts monochlorpropionlc acid and 80 parts of caustic soda. Theprocess is carried out in the same manner as described in the previousexamples and there is produced a product having the same formula as thatof Example A, except that CnHas 1s substituted for C11H23 and CzH4-COONafor the CH2-COONa therein, and is hereinafter known as product F.

EXAMPLE G 290 parts dodecyl benzoic acid and 104 parts of reactant A arecondensed in the manner described in Example D and the resultant mass isprocessed in the manner of Example D, whereby there is produced a novelcompound having the same formula as that of Example A, except thatC12H25C6H4 is substituted for C11H23 therein, and is hereinafter knownas product G.

EXAMPLE H 228 parts of myristic acid and 104 parts reactant A arereacted in the manner described in Example D and the resultant mass isprocessed in the manner of Example D, whereby there is produced astarting material hereinafter known as product H, and having the sameformula as that of Example A, except that C13H21 is substituted forC11H2s therein.

Still another type of method may be employed to produce some of thesecompounds, and examples thereof are shown hereinafter merely in anillustrative and not in a limiting sense.

EXAMPLE I 1 mol of lauric fatty acid and 1 mol of ethylenediamine(NH2CzH4NH2) are added together and then heated in the presence of aninert solvent such as toluol in amounts sufiicient to dissolve the same.This solution is maintained at a temperature of approximately 110 C.This heating is carried out under a condenser through which pass vaporswhich consist of some of the solvent and water of reaction as well assmall amounts of unreacted amine. These products are caught in acollector from which the water of reaction is removed and the condensedtoluol and collected amine are returned to the reacting vessel. Thetemperature of the mass is maintained at 110 C. under the aforesaidconditions until 0.9 mol of water is collected. Then a vacuum ofapproximately 90 mm. of mercury is applied to the reacting vessel andthe temperature maintained at 110 C. until all of the solvent and anadditional 0.1 mol of water have been removed. To the resulting mass isadded 1 mol of monochloracetic acid and this mixture is heated to atemperature of approximately 120 C., whereupon the temperature of themass will spontaneously rise to 170 C. By the application of externalheat themass is maintained at said temperature at approximately 170 C.until a one part sample thereof when dissolved in 100 parts of aqueoussolution of sodium hydroxide having a pH of approximately 9 provides aclear solution. 1 mol of this mass so produced is added to an aqueoussolution containing 1 mol of sodium hydroxide. The entire mass is heatedto approximately C. whereupon there is formed the sodium salt of saidmass, having the following formula:

The aforesaid salt, whose structural formula is shown in this examplemay be produced in still another Way. In-

stead of adding the monochloracetic acid at the stage previously shown,there first may be prepared an aqueous solution containing 2 mols ofsodium hydroxide and one mol of monochloracetic acid. The temperature ofthis solution is reduced below 15 C. and preferably 5 to 10 C. and whilemaintained at said reduced temperature and being constantly agitatedthere is added thereto one mol of the lauric acid-ethylene diaminereaction mass. While being constantly agitated, the temperature of themass is raised over a one-hour period to about C. Then the temperatureof this constantly agitated mass is maintained at 95 C. for anadditional 3 hours or until a sample thereof in parts of water will beclear and the pH is no longer subject to change on further heating ofthe mass at that temperature.

1 mol of the last defined compound is added to a solution containing onemol of caustic soda and one mol of chlorhydrin dissolved in water at atemperature not exceeding 15 C. and preferably between 5 to 10 C. Afterthe addition at said low temperature, the mass is continuously agitatedand while in the state of agitation, its temperature is raised overabout a one hour period to 95 C. and is further continuously agitatedand maintained at said temperature for an additional 3 hours, all ofthis being done under a reflux condenser. During said 3 hour period, thepH of the mass continuously decreases. At the expiration of that 4 hourperiod the pH of 1 part of the mass when dissolved in 100 parts of Waterwill be 8.5. The 1 part sample when dissolved in 100 parts of water andhaving a pH of 8.5 in the water, provides a clear solution and is thesame product as that of Example A.

EXAMPLE K By following the same procedure as that set forth in Example Iwith the only difference being that one mol of glycerine chlorhydrin(CH2Cl-CHOHCH2OH) is substituted for the mol of ethylene chlorhydrinthere is produced another one of my starting materials, hereinafterknown as product K, and having a formula the same as that of Example A,except that CI-IzCHOHCI-IzOH is substituted for C2H4OI-I of Example A.

EXAMPLE L By following the same procedure as that set forth in Example Iwith the only difference being that one mol of pentaerythritolchlorhydrin (CH2ClC(CH2OH)3) is substituted for the mol of ethylenechlorhydrin there is produced another one of my starting materials,hereinafter known as product L, and having a formula the same as that ofExample A, except that CH2C(CH2OH)2OH is substituted for -C2H4OH ofExample A.

7 EXAMPLE M By following the same procedure as that set forth in ExampleI with the only difference being that one mol of dimethoxylhydroxyketone chlorhydrin (ClCH2COCH2--OH) EXAMPLE N By following the sameprocedure as that set forth in Example I with the only difference beingthat, instead of employing one mol of ethylene chlorhydrin, there isemployed one mol of the following compound:

ClCHzC O CH there is produced another one of my starting materials,hereinafter known as product N, and having the same formula as that ofExample A, except that CHZCOCHOHOH is substituted for C2H4OH of ExampleA. The particular ketone reactant employed in this example may beproduced by the distillation of one mol of dihydroxy acetic acid, onemol of hydroxy acetic acid and one mol of calcium carbonate after whichthe distillation product is chlorinated.

EXAMPLE P By following the same procedure as that set forth in Example Iwith the only difference being that one mol of monochlorlactic acid isemployed instead of the one mol of monochloracetic acid so that there isproduced still another of my starting material, hereinafter known asproduct P, having the same formula as that of Example A, except thatCHzCHOHCOONa is substituted for CHzCOONa of Example A. In thisproduction I prefer to use the aqueous method as set forth in Example I.

EXAMPLE Q Employing the same procedure as that set forth in Example A,except that 1 mol of capric acid and 1 mol of reactant B and 1 mol ofmonochlorproprionic acid are substituted for the lauric acid, reactant Aand monochloracetic acid, so that there is produced a starting material,hereinafter known as product Q, having the following formula:

EXAMPLE R Employing the same procedure as that set forth in Example A,except that 1 mol of stearic acid 1 mol of reactant C and 1 mol ofmonochlorlactic acid are employed in place of the lauric acid, reactantAand monochloracetic acid, there is provided a starting material,

, (llHa l? (1311; (ll-CH3 Ol7H35 CON?-CH2"N CHr-OH CH3 CHzCHOH-COONaEXAMPLE S Employing the same procedure as that set forth in Example A,except that 1 mol of myristic acid, 1 mol of reactant D and 2 mols ofpotassium hydroxide are used in place of the lauric acid, reactant A andcaustic soda are used to provide starting material, hereinafter known asproduct S, having the following formula:

111 CHzCHOHCH2OH C aHz7-CON-CHzCHOHCH N OHz-COOK EXAMPLE T Employing thesame procedure as that set forth in Example A, except that 1 mol ofcapric acid, 1 mol of reactant E, and 1 mol of monochlorethoxyaceticacid are used in place of the lauric acid, reactant A and monochloracetic acid to provide starting material, hereinafter known asproduct T, having the following formula:

Employing the same procedure as that set forth in Example T, except that1 mol of oleic acid, 1 mol of reactant F and 1 mol ofmonochloracetoacetic acid in place of the lauric acid, reactant A andmonochloracetic acid to provide starting material, hereinafter referredto as product U, having the following formula:

EXAMPLE V Employing the same procedure as that set forth in Example A,except that in place of the lauric acid, reactant A and caustic soda,substitute 1 mol of dodecylbenzenemonocarboxylic acid (C1zH25CsH-1COOH),1 mol of reactant G and 2 mols of potassium hydroxide, to providestarting material, hereinafter known as product V, having the followingformula:

The specific monocarboxylic acids, as well as the specificmonohalomonocarbylic acids employed in certain examples, may be replacedby others as may be the various other reactants in the specific examplesto provide 'a great number of other starting materials, which differfrom those set forth in the examples heretofore set forth.

Prior to this invention, it was known that cationic surface activeagents and anionic surface active agents when together in aqueoussolution resulted in the production or formation of water insolublecompounds; and that adding an anionic surface active agent to an aqueoussolution of another anionic surface active agent resulted in a merephysical combination of said agents and that no reaction would occurbetween them.

Said amino acid metal salts normally behave anionically in aqueoussolutions having a pH above 7, and consequently it was expected thatsaid amino acid metal salts when in aqueous solution together withanionic surface agents that they would be combined physically min onlyand that no chemical reaction would occur therebetween. In the course ofmy experimentations, I have discovered that said amino acid metal saltscould be reacted with certain anionic surface active agents at a pHabove 7 to produce water-soluble reaction products. Not only did I makesaid discovery, but I further discovered that water solutions of suchreaction products had viscosities greater than corresponding aqueoussolutions of the amino acid metal salts and also exhibited betterfoaming characteristics than did said amino acid metal salts in very lowdilutions under extreme water hardness conditions. Said reactionproducts are non-toxic and non-irritating to the human skin. They havebeen found eminently useful as general utility detergents, such as forcar washing, dish washing, clothes Washing, etc. Said amino acid metalsalts when used as components of shampoos sometimes caused slightirritation or stinging of the eyes when such shampoos were used andwater solutions thereof accidentally reached the eyes. I have furtherdiscovered that the reaction products of this invention causedpractically no irritation or stinging of the eyes when so employed.

According to this invention, one or a combination of two or more of saidamino acid metal salts of the general structural Formula I are reactedwith one or a combination of two or more anionic surface active agentsof the following general structural Formula H to provide novel,water-soluble compounds having the following general structural FormulaIII, and having high wetting, detergency and surface active propertiesand capable of providing voluminous and stablefoams in aqueoussolutions, and which aqueous solutions are substantially non-irritatingto the skin and eyes of normal human beings.

F rmula II RsX-M Formula III Rl ra -on n-oo-rL -Rt-N H Rz-COOM RsXwherein R3 is a hydrocarbon radical, either aliphatic containing 6-18carbon atoms, or aliphatic-aromatic con sisting of a benzene ring or anaphthalene ring having an aliphatic radical of 6-18 carbon atomsattached thereto; X is 0303 or S03; and R, R1, R2 and M have beenheretofore defined in Formula I.

According to this invention, I react a compound of Formula I with acompound of Formula H to provide the novel and highly useful compoundsof Formula III. In general this reaction is carried out in a solutioncontaining compounds I and II and to which a quantity of an acidic agentsuch as a strong mineral acid, as for example hydrochloric, sulphuric orits equivalent, has been added to lower the pH of the solution to avalue of approximately 7 to approximately 9 and while maintaining themass at a temperature between approximately 100-200 F. In this reactionunder the aforesaid conditions, the compounds of Formula III areproduced, said compounds having high water solubility in spite of thefact that the number of carbon atoms in R3 is 6 or more. Such compoundsof Formula III have an unexpected extremely high water-solubility, whilethe corresponding salts of cationic compounds are water-insoluble. Theresultant aqueous solution can be used directly as a surface activeagent, wetting agent or detergent for the purposes indicated for theamino acid metal salts. While the quantities of the compound of FormulaI and compound of Formula II may be equimolecular for good yield ofcompounds of Formula III, I may employ an excess of either, and ingeneral the mole ratio of a compound of Formula I to compound of FormulaH may be 2 moles of the former to 1-3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out anaspect-of thisinvention is to first dissolve a compound of Formula I inwater and then the pH thereof is adjusted to approximately 12-13(measured electrically) by the addition of aqueous caustic soda ifrequired so that when a compound of Formula II is added thereto, the pHof the solution of I and II will be at least 10 and generally -11. Thetemperature of said solution is raised to 100-200 F. and preferably infactory practice to approximately F. Then a quantity of a compound ofFormula II is dissolved in water in a separate container and thissolution is added to said first solution and the mass is maintained insaid temperature range while being constantly stirred, and an acidicagent is added thereto to reduce the pH thereof to a value below 10 andin the range of approximately 7 to 9, and preferably of approximately8.2 to approximately 8.7. At the end of the acidic agent addition,'the'stirring is continued and the temperature of the mass maintained forabout 10- 20 minutes after which the solution is allowed to cool and isa finished product.

The following are specific examples merely given by way of illustratingthe invention and are not to be taken by way of limitation, all partsbeing given by weight unless otherwise specified.

EXAMPLE 1 An aqueous solution of 400 parts of product A in 600 parts ofwater is heated to approximately 1'40 F. and its pH (measuredelectrically) is adjusted by the addition of aqueous caustic soda to12-13. While being constantly stirred and maintained at thattemperature,

there is added a solution of 290 parts of sodium salt of lauryl sulfate:

in 450 parts of water. Then while stirring and the temperature ismaintained there is added thereto between about 30-40 parts ofhydrochloric acid solution (32%) whereby the pH of the mass is loweredto a value in the range of 8.2 to 8.7. Stirring is continued and thetemperature maintained for about 10 minutes more. The resultant productis a solution of the novel reaction product having the followingformula:

CH -C OONa acid solution (32%) is variable to lower the pH to valuesindicated in Example 1 to obtain the novel re action products of saidExamples 3-36.

EXAMPLE 3 400 parts of product A in 600 parts of water. parts of stearylsulfonate sodium salt:

C1sH3'r-SOsNa in 700 parts of water.

zyrs-nss 350 parts of product C in 650 parts'of water. parts of dodecylbenzene sulfonate sodium salt:

C12 H25CeH4SO3-Na in 500 parts of Water.

FORMULA OF NOVEL REACTION PRODUCT oguhon 400 parts of product A in 600parts of water. parts of hexylnaphthene sulfonate sodium salt:

S a-Na oHn in 450 parts of water.

FORMULA OF NOVEL REACTION PRODUCT H CzH4-OH O 11Hza-C Ol I-OzH4N H OH2'C0 ONa EXAMPLE 6 400 parts of product Q in 400 parts of water. parts ofhexyl sulfate sodium salt:

CsI-I13-OSO3--Na in 400 parts of water.

FORMULA OF NOVEL REACTION PRODUCT OH: CH3 OHQGHOH CQH1QCOI TOH OHN CH HGzH4--COONa CrH13O 0:;

EXAMPLE 7 550 parts of product R in 850 parts of water. parts of decylbenzene sulfonate sodium salt:

EXAMPLE 8 450 parts of product S. in 500 parts of water. parts of octylbenzene sulfate potassium salt:

CaHi'z-CeH4SO3-K in 500 parts of water.

FORMULA OF NOVEL REACTION PRODUCT H GHZCHOHCHT'OH 450 parts of product Tin 500 parts of water. parts of decyl sulfate sodium salt:

C1oH21SO3-Na in 600 parts of water.

FORMULA OF NOVEL REACTION PRODUCT C3137 C2H4OC2H4- 550 parts of productU in 850 parts of water. parts of heptyl benzene sulfonate sodium salt:

C'1H15C6H4SOaNa in 450 parts of water.

FORMULA OF NOVEL REACTION PRODUCT (34110 CHzOOCHz-OH C11H3a-CONCH:OHOHCHr-N H GHiCOOHz-OOON5 C'lH1 CaH4-S Os EXAMPLE 11 550 parts ofproduct V in 800 parts of water. parts of tridecyl sulfonate potassiumsalt:

C13H2'zSO3Na in 450 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CZHE O2H4OH C1QH25-COH4O ONCH2O OOHfl-N H GHQ-0001i C1aHz1SOa EXAMPLES 12-16 Employing the same procedureas that set forth in Example 1, except that products B, K, L, M, and Nare respectively substituted for product A to provide novel reactionproducts which differ from the novel reaction product whose formula isshown in Example 1, by substituting for the C2H@-OH radical thereof, thefollowing respective radicals: CzH4OC2H4-OH,

CH2CHOHCH2OH, CH2C(CH2OH) z-QH,

CH2COCH2OH, CH2COCHOHOH.

EXAMPLES 17-20 Employing the same procedure as that set forth in Example1, except that products D, E, G and H are respectively substituted forproduct A to provide novel reaction products, which differ from thenovel reaction product whose formula is shown in Example 1, bysubstituting for the CuHza radical attached to the CO group thereof thefollowing respective radicals: C1'zH31, C5H11,

and C13H27.

EXAMPLE 21 Employing the same procedure as that set forth in Example 1,except that product P is substituted for product A to provide a reactionproduct which diifers from the novel reaction product, whose formula isshown in Example 1, by substituting. forthe CH-COONa radical thefollowing radical: CHz-CHOPL-COONa.

EXAMPLES 22.AND 23 Employing the same procedure as that set forth inExample 1, except that products C and F respectively are substituted forproduct A to provide novel reaction products which diifer from the novelreaction product Whose formula is shown in Example 1, by substitutingfor the CHz-COONa and also substituting C9H19 and C17H35 respectivelyfor C11H23.

EXAMPLES 24-36 Employing the same procedure as that set forth in Example3, except that, instead of product A, there are respectively substitutedcompounds which are the same as product A, except that the H of the NHattached directly to the CO group thereof is replaced by the followingrespective radicals: -CH3, -C2H5, C3H7, C4H9, -C2HOH, -CH2CHOHCH2,-CHOHCHOHCH2OH, -C2H4OCH3, -C2H4OC2H4OH, -CH2CHOHOC2H5, CH2COCH3,-C2H4COC2H4OH, -CH2OHCOC2H5; whereby there are produced a number ofother novel reaction products whose formulas are the same as the formulaof the novel reaction product whose formula is within the definition ofFormula III and shown in Example 3, except that the aforesaid respectiveradicals replace the H of the NH connected directly to the CO thereof.

Following the same procedure as that set forth in Example 1 andemploying 1 mol of any of said other starting materials, such asproducts B-H, I-N, P-V, respectively, and 1 mol of any of the otherspecific compounds of Formula II employed in Examples 1-36, a greatnumber of other novel reaction products whose formulas are that ofFormula III may be produced; and in addition, the specific reactantsemployed may differ from those employed herein, in varying R, R1, R2,and R3 within the definitions thereof, to provide a great number ofother compounds of Formula IH.

It is to be understood that instead of first adjusting the pH of thecompound of Formula I to 12-13 before the addition of the compound ofFormula H, any other method may be employed to obtain the conditionwhereby the pH of the solution of I and II is at least and preferably10.5-11 before the addition of the acidic agent to lower the pH of themass to approximately 7 to approximately 9. For example, I and II may bedissolved together and this solution may, by the addition of causticsoda when required, have its pH adjusted to at least 10, and then at100-200 F. is ready for the addition of the acidic agent to lower its pHto approximately 7 to approximately 9. If desired, the required amountof acidic agent may be added either before or after the solution of pHof at least 10 is brought to a temperature in the range of IOU-200 F.

Since certain changes in carrying out the aforesaid processes andcertain modifications in the compositions which embody the invention maybe made without departing from its scope, it is intended that all mattercontained in the description shall be interpreted as illustrative andnot in a limiting sense.

It is also to be understood that the following claims are intended tocover all the generic and specific features of the invention hereindescribed, and all statements of the scope of the invention which as amatter of language might be said to fall therebetween.

I claim:

1. A compound of the following formula:

in which R is a hydrocarbon radical of 4 to 18 carbon atoms; R: is anorganic group selected from the class consisting of (a) aliphatichydrocarbon groups of 1-4 carbon atoms; ('b) hydroxy substitutedaliphatic hydrocarbon groups of 1-4 carbon atoms, (c) aliphatic ethergroups, each of said other groups having an ether oxygen linkage thereinand otherwise being hydrocarbon of 2-4 carbon atoms, (d) aliphatic ethergroups, each of said groups having an ether oxygen linkage therein andotherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e)aliphatic keto groups, each of said groups having a carbonyl linkagetherein and otherwise being hydrocarbon of 2-4 carbon atoms, (1)aliphatic keto groups, with each of said groups having a carbonyllinkage therein and otherwise being hydroxy substituted hydrocarbon of2-4 carbon atoms; R1 is selected from the group consisting of hydrogenand monovalent radicals otherwise defined in said (a)-(f); R3 is ahydrocarbon radical selected from the class consisting of (h) aliphatichydrocarbon radical-s of 6-18 carbon atoms and (i) aliphatic-aromatichydrocarbon radicals consisting of benzene and naphthalene groups, eachgroup having an aliphatic hydrocarbon radical of 6-18 carbon atomsattached thereto; X is selected from the group consisting of S03 and0803; and M is an alkali metal.

2. A compound of the following formula:

Rsin which R is a hydrocarbon radical of 4-18 carbon atoms and R3 is analiphatic hydrocarbon radical of 6-18 carbon atoms, and X is selectedfrom the group consisting of S03 and 0803.

3. A compound of the following formula:

in which R is a hydrocarbon radical of 4-18 carbon atoms and R4 is analiphatic hydrocarbon radical of 6-18 carbon atoms.

4. A compound of the following formula:

in which R is a hydrocarbon radical of 4-18 carbon atoms and R4 is analiphatic hydrocarbon radical of 6-18 carbon atoms.

5. A compound of the following formula:

III CrH4OH C11H23-C ONC aH4-N\ H I CHzCOONa RaX in which R3 is analiphatic hydrocarbon radical of 6-18 carbon [atoms and X is selectedfrom the group of SO: and 0503.

6. A compound of the following formula:

III C2H4OH CuHza-C O-NC2H4-N CHPCOONB Cn u T. A compound of thefollowing formula:

CEHA-OH GQHm-C O-Ib-CzHv-N H GHQ-C O ONa References Cited in the file ofthis patent UNITED STATES PATENTS Neelmeier et all Aug. 29, 1933Schoeller Dec. 28, 1934 I Munz et a1 Feb. 3, 1942 Mauersberger Sept. 14,1943 Iaccard Mar. 6, 1951 Katzman June 3, 1952

1. A COMPOUND OF THE FOLLOWING FORMULA: